Foaming composition for washing and treating hair and/or scalp based on an active principle

ABSTRACT

The invention concerns a foaming composition for washing and treating hair and/or scalp essentially characterized in that it contains in an aqueous medium: at least an active principle selected among corticoids and retinoids; at least an anionic surfactant; at least an amphoteric surfactant; and a pro-penetrating agent.

This application is a continuation of application Ser. No. 09/709,477,filed Nov. 13, 2000 (issued as U.S. Pat. No. 7,316,810 on Jan. 8, 2008),which is a continuation of PCT/FR99/01452, filed Jun. 17, 1999, whichdesignated the U.S. and claims benefit of FR 98/07802, filed Jun. 19,1998, the entire contents of each of which are hereby incorporated byreference in this application.

The present invention relates to novel foaming compositions for washingand treating the hair and/or scalp, comprising at least one activeprinciple chosen from corticosteroids and retinoids, one anionicsurfactant, one amphoteric surfactant and one propenetrating agent, andto the treatment process employing such compositions.

Psoriasis is one of the commonest skin ailments among all chronic skindiseases. This disease is found in 1.4 to 2.9% of the population. Thescalp is one of the favored sites for psoriasis; the latter causesessentially erythemas, desquamations, hyperkeratoses or pruritides andcan also be responsible for a reduction in hair density. The treatmentsused to date involve salicylic acid, local steroids, anthralin, or coalor wood tar. These treatments are unpleasant, in particular when tar isapplied, and require lengthy applications, in particular when hairointments are used.

For the purpose of improving the quality of life for the patient,without however decreasing the therapeutic effect of the treatment,foaming compositions comprising corticosteroids have been developed.More particularly, the application time of these foaming compositions isreduced with respect to the conventional treatment.

Patent BE 84515 discloses a composition comprising hydrocortisone in asolvent mixture composed of 15 to 60% of aliphatic alcohol, 15 to 60% ofpropylene glycol and of 5 to 60% of a third solubilizing agent takenfrom the group consisting of 2-hydroxyethyl salicylate, dipropyl ketoneand dimethylcocobenzylammonium chloride.

Patent EP 0 325 949 discloses a solution comprising at least 2.5% ofcorticosteroids, from 25 to 80% of a nonionic surfactant, from 0 to 70%of ethanol, from 0 to 70% of propylene glycol and an antimicrobialagent.

Nevertheless, the solvents present in these compositions have a tendencyto evaporate very rapidly. Furthermore, the fluidity of thesecompositions renders the application difficult and it is often necessaryto apply these compositions by rubbing in order to allow effectivepenetration of the active principles, the consequence of which is toirritate the epidermis even more, or to apply these compositions and toallow them to act for several hours, which is annoying to the patient.

To avoid evaporation of the solvent, provision has been made, in PatentWO 9627376, for a foam comprising a corticosteroid, a foam-breakingagent, a propellant and buffer. The foam-breaking agent is composed ofan aliphatic alcohol, of water, of a fatty alcohol and of a nonionicsurfactant. Nevertheless, when these foams are applied to keratinousfibers, their resulting esthetic appearance is not satisfactory and thescalp lying under the keratinous fibers may be insufficiently treated.

The Applicant Company has looked for compositions which do not exhibitthe abovementioned disadvantages, that is to say a composition whichmakes it possible to improve the penetration of the active principlewhile being particularly easy to use and exhibiting good cosmeticproperties.

The Applicant Company has now developed a foaming composition whichexhibits the properties mentioned above.

The compositions of the present invention, while making possible goodpenetration of the active principles, also exhibit an improvement in thecosmetic performances of the compositions for the treatment of skinailments or of the hair, the compositions of the invention leaving thehair soft and manageable and not rendering it greasy. Furthermore, thesecompositions are easy to rinse out.

The Applicant Company has also found that the foaming compositions ofthe present invention surprisingly make it possible to obtain a foamwhich exhibits improved characteristics of volume and of compactnesswith respect to the foaming compositions for the treatment of skinailments or of the scalp of the prior art.

It has also been found that, surprisingly, the compositions which aresubject matters of the present invention are stable over time, making itpossible to prevent the precipitation of the active principles, and thusremain clear.

One of the subject matters of the invention is thus composed of afoaming composition for washing and treating the hair and/or the scalp.

Another subject matter of the invention is a process for washing andtreating the hair and/or the scalp employing such a composition.

A subject matter of the invention is also a composition according to theinvention for its application as medicament.

A subject matter of the invention is also the use of the compositions ofthe invention as medicament and for the manufacture of a medicamentintended to treat skin ailments or hair.

Other subject matters of the invention will become apparent on readingthe description and the examples which follow.

The foaming composition for washing and treating the hair and/or thescalp is essentially characterized in that it comprises, in an aqueousmedium:

-   -   at least one active principle chosen from corticosteroids and        retinoids,    -   at least one anionic surfactant,    -   at least one amphoteric surfactant, and at least one        propenetrating agent.

In the context of the present invention, the corticoids can be chosenfrom alclometasone dipropionate, amcinonide, beclomethasonedipropionate, betamethasone benzoate, betamethasone dipropionate,betamethasone valerate, budesonide, clobetasol propionate, preferablyclobetasol 17-propionate, clobetasol butyrate, desonide, desoximetasone,dexamethasone, diflorasone diacetate, diflucortolone valerate,flurandrenolone, fluprednidene acetate, fluocortolone, fluocortin butyl,fluocinonide, fluocinolone acetonide, fluclorolone acetonide,flumetasone pivalate, feudiline hydrochloride, flumetholon, halcinonide,hydrocortisone, hydrocortisone acetate, hydrocortisone butyrate,hydrocortisone valerate, methylprednisolone acetate, mometasone furoate,methylprednisolone, prednisolone or triamcinolone acetonide or frompharmaceutically acceptable mixtures of the latter.

The retinoids can be chosen from all-trans-retinoic acid, also known astretinoin or vitamin A acid, adapalene, isotretinoin, retinol, that isto say vitamin A, and its derivatives, such as retinol acetate,palmitate or propionate, motretinide, etretinate, acitretin, zincall-trans-retinoate, third generation retinoids obtained by the additionof cyclic groups to the polyene side chain, also known as arotinoids, orsynthetic retinoids, or from pharmaceutically acceptable mixtures of thelatter.

Preference is given, among the retinoids, to adapalene,4-[7-(1-adamantyl)-6-methoxyethoxymethoxy-2-naphthyl]benzoic acid,2-hydroxy-4-[3-oxo-3-(3-tert-butyl-4-methoxyphenyl)-1-propynyl]benzoicacid and4-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthylthio)benzoic acid.

The active principle which is particularly preferred among thecorticoids is clobetasol 17-propionate.

The active principle can be used in proportions of 0.001 to 5%,preferably between 0.01 to [sic] 0.3% and more preferably between 0.05and 0.1% by weight with respect to the total weight of the composition.

In the context of the present invention, the nature of the anionicsurfactants does not assume a really critical character.

Thus, mention may in particular be made, by way of example of anionicsurfactants which can be used, alone or mixed, of the salts (inparticular alkali metal, especially sodium, salts, ammonium salts, aminesalts, aminoalcohol salts or magnesium salts) of the followingcompounds: alkyl sulfates, alkyl ether sulfates, alkylamido ethersulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkyl phosphates, alkylamide sulfonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkylsulfosuccinamates, alkyl sulfoacetates, alkylether phosphates, acylsarcosinates, acylisethionates and N-acyltaurates,the alkyl or acyl radical of these various compounds preferablycomprising from 12 to 20 carbon atoms and the aryl radical preferablydenoting a phenyl or benzyl group.

Mention may also be made, among the anionic surfactants which canfurther be used, of the salts of fatty acids, such as the salts ofoleic, ricinoleic, palmitic and stearic acids, the acids of coconut oilor of hydrogenated coconut oil, or acyllactylates, the acyl radical ofwhich comprises 8 to 20 carbon atoms. Use may also be made of weaklyanionic surfactants, such as alkyl D-galactosideuronic acids and theirsalts, as well as polyoxyalkylenated (C₆-C₂₄)alkyl ether carboxylicacids, polyoxyalkylenated (C₆-C₂₄)alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄)alkylamido ether carboxylic acids and theirsalts, in particular those comprising from 2 to 50 ethylene oxidegroups, and their mixtures.

Among the anionic surfactants, it is preferable to use, according to theinvention, alkyl sulfate or alkyl ether sulfate salts or their mixtures.

More particularly, it is preferable to use sodium lauryl ether sulfate(2 mol EO), in particular that sold under the name “Texapon N70®”,sodium lauryl ether sulfate, particularly that sold under the name“Sipon AOS 225 UP®”, and sodium lauryl sulfate, in particular that soldunder the name “Texapon K 12®”.

These anionic surfactants can be used in proportions of between 0.05 and50%, preferably between 1 and 30% and more preferably between 2 and 25%of Active Material (A.M.) by weight with respect to the total weight ofthe composition.

The amphoteric surfactants, the nature of which does not assume acritical character in the context of the present invention, may be inparticular derivatives of aliphatic secondary or tertiary amines inwhich the aliphatic radical is a linear or branched chain comprising 8to 22 carbon atoms and comprising at least one water-solubilizinganionic group (for example carboxylate, sulfonate, sulfate, phosphate orphosphonate); mention may also be made of (C₈-C₂₀)alkyl betaines,sulfobetaines, (C₉-C₂₀)alkyl amido(C₁-C₆)alkyl betaines or (C₈-C₂₀)alkyl amido(C₁-C₆) alkyl sulfobetaines.

Mention may be made, among the amine derivatives, of the products soldunder the Miranol names, as disclosed in U.S. Pat. No. 2,528,378 andU.S. Pat. No. 2,781,354 and with structures:R₂—CONHCH₂CH—N(R₃)(R₄)(CH₂COO⁻)in which: R₂ denotes an alkyl radical derived from an acid R₂—COOHpresent in hydrolyzed coconut oil or a heptyl, nonyl or undecyl radical,R₃ denotes a betahydroxyethyl group and R₄ denotes a carboxymethylgroup;and R₅—CONCH₂CH₂—N(B)(C)in which:B represents —CH₂CH₂OX′, C represents —(CH₂)_(z)—Y′, with z=1 or 2,X′ denotes the —CH₂CH₂—COOH group or a hydrogen atomY′ denotes —COOH or the —CH₂—CHOH—SO₃H radicalR₅ denotes an alkyl radical of an acid R₉—COOH present in hydrolyzedlinseed oil or coconut oil, an alkyl radical, in particular a C₇, C₉,C₁₁ or C₁₃ radical, a C₁₇ alkyl radical and its iso form, or anunsaturated C₁₇ radical.

These compounds are classified in the CTFA dictionary, 7th Edition,1998, under the names Disodium Cocoamphodiacetate, DisodiumLauroamphodiacetate, Disodium Caprylamphodiacetate, DisodiumCapryloamphodiacetate, Disodium Cocoamphodipropionate, DisodiumLauroamphodipropionate, Disodium Caprylamphodipropionate,Lauroamphodipropionic Acid and Cocoamphodipropionic Acid.

Among the amphoteric surfactants, corobetaines are particularlypreferred and more particularly cocamidopropyl betaine, in particularthat sold under the name “Tegobetaine F50®”, cocamidopropylhydroxysultaine, in particular that sold under the name “Amonyl 675SB®”, and cocoyl betaines, in particular those sold under the names“Dehyton AB 30®” and “Chimexane HC®”.

These amphoteric surfactants can be used in proportions of between 0.01and 30%, preferably between 0.5 and 20% and more preferably between 1and 15% as A.M. by weight with respect to the total weight of thecomposition.

The ratio of the proportion as A.M. of the anionic surfactants to theproportion as A.M. of the amphoteric surfactants is preferably between 1and 20 and more preferably between 2 and 10.

The propenetrating agent, which makes it possible to facilitate thepenetration of the active principles, preferably dissolves the activeprinciple present in the composition according to the invention. Moreparticularly, it is chosen from volatile C₁-C₄ alcohols, such as ethanolor isopropanol, from polyhydric alcohols, such as propylene glycol, andfrom glycol ethers, such as ethoxydiglycol.

The preferred propenetrating agent in the context of the presentinvention is ethanol.

The propenetrating agents can be used in concentrations of between 0.1and 25% and preferably of between 5 and 10% by weight with respect tothe total weight of the composition.

The ratio of the proportion as A.M. of the anionic surfactants to theproportion of the propenetrating agents is preferably between 0.1 and 10and more preferably between 0.5 and 5 and more preferably still between1 and 2.

The compositions which are subject matters of the present invention canbe thickened and their cosmetic properties improved by adding thereto,for example, cationic polymers, acrylic polymers or cellulosederivatives which are or are not quaternized.

The cationic polymers which can be used in accordance with the presentinvention can be chosen from all those already known per se as improvingthe cosmetic properties of hair treated with detergent compositions,namely, in particular, those disclosed in Patent Application EP-A0,337,354 and in French Patent Applications FR-A-2,270,846, 2,383,660,2,598,611, 2,470,596 and 2,519,863.

More generally still, within the meaning of the present invention, theexpression “cationic polymer” denotes any polymer comprising cationicgroups and/or groups which can be ionized to cationic groups.

The preferred cationic polymers are chosen from those which compriseunits comprising primary, secondary, tertiary and/or quaternary aminegroups, which can either form part of the main polymer chain or becarried by a side substituent directly connected to the latter.

The cationic polymers used generally have a number molecular mass ofbetween 500 and 5H 10⁶ approximately and preferably of between 10³ and3H 10⁶ approximately.

Mention may more particularly be made, among cationic polymers, ofquaternized proteins (or protein hydrolysates) and polymers of thepolyamine, polyaminoamide and poly(quaternary ammonium) type. These areknown products.

The quaternized proteins or protein hydrolysates are in particularchemically modified polypeptides carrying quaternary ammonium groups atthe chain end or grafted onto the chain. Their molecular mass can vary,for example, from 1500 to 10,000 and in particular from 2000 to 5000approximately. Mention may in particular be made, among these compounds,of:

collagen hydrolysates carrying triethylammonium groups, such as theproducts sold under the name “Quat-Pro E” by Maybrook and called in theCTFA dictionary, “Triethonium Hydrolyzed Collagen Ethosulfate”;

collagen hydrolysates carrying trimethylammonium andtrimethylstearylammonium chloride groups, sold under the name of“Quat-Pro S” by Maybrook and called, in the CTFA dictionary,“Steartrimonium Hydrolyzed Collagen”;

animal protein hydrolysates carrying trimethylbenzylammonium groups,such as the products sold under the name “Crotein BTA” by Croda andcalled, in the CTFA dictionary, “Benzyltrimonium Hydrolyzed AnimalProtein”;

protein hydrolysates carrying, on the polypeptide chain, quaternaryammonium groups comprising at least one alkyl radical having from 1 to18 carbon atoms,

Mention may be made, among these protein hydrolysates, inter alia, of:

“Croquat L”, the quaternary ammonium groups of which comprise a C₁₂alkyl group;

“Croquat M”, the quaternary ammonium groups of which comprise C₁₀-C₁₈alkyl groups;

“Croquat S”, the quaternary ammonium groups of which comprise a C₁₈alkyl group;

“Crotein Q”, the quaternary ammonium groups of which comprise at leastone alkyl group having from 1 to 18 carbon atoms.

These various products are sold by Croda.

Other quaternized proteins or hydrolysates are, for example, thosecorresponding to the formula:

in which X⁻ is an anion of an organic or inorganic acid, A denotes aprotein residue derived from collagen protein hydrolysates, R₅, denotesa lipophilic group comprising up to 30 carbon atoms and R₆ represents analkylene group having 1 to 6 carbon atoms. Mention may be made, forexample, of the products sold by Inolex under the name “Lexein QX 3000”,called “Cocotrimonium Collagent [sic] Hydrolysate” in the CTFAdictionary.

Mention may also be made of quaternized plant proteins, such as wheat,maize or soya proteins: mention may be made, as quaternized wheatproteins, of those sold by Croda under the names “Hydrotriticum WQ orQM”, called “Cocodimonium Hydrolysed Wheat Protein” in the CTFAdictionary, “Hydrotriticum QL”, called “Laurdimonium Hydrolysed wheatProtein” in the CTFA dictionary or “Hydrotriticum QS”, called“Steardimonium Hydrolysed Wheat Protein” in the CTFA dictionary.

The polymers of the polyamine, polyamidoamide or poly(quaternaryammonium) type which can be used in accordance with the presentinvention which can be mentioned in particular are those disclosed inFrench Patents No. 2,505,348 or 2,542,997. Mention may be made, amongthese polymers, of:

(1) optionally quaternized vinylpyrrolidone/dialkylaminoalkyl acrylateα-methacrylate [sic] copolymers, such as the products sold under thename “Gafquat” by ISP, such as, for example, Gafquat 734, 755 or HS100,or else the product called “Copolymer 937”. These polymers are disclosedin detail in French Patents 2,077,143 and 2,393,573.

(2) cellulose ether derivatives comprising quaternary ammonium groupsdisclosed in French Patent 1,492,597 and in particular the polymers soldunder the names “JR” (JR 400, JR 125, JR 30M) or “LR” (LR 400, LR 30M)by Union Carbide Corporation. These polymers are also defined in theCTFA dictionary as quaternary ammoniums of hydroxyethylcellulose whichhas reacted with an epoxide substituted by a trimethylammonium group.

(3) cationic cellulose derivatives, such as the copolymers of celluloseor the cellulose derivatives grafted with a water-soluble quaternaryammonium monomer and disclosed in particular in U.S. Pat. No. 4,131,576,such as hydroxyalkyl celluloses, for example hydroxymethyl-,hydroxyethyl- or hydroxypropyl-celluloses, grafted in particular with amethacryloylethyltrimethylammonium, methacrylmidopropyltrimethylammoniumor dimethyldiallylammonium salt.

The marketed products corresponding to this definition are moreparticularly the products sold under the name “Celquat SC 240”, “CelquatL 200” and “Celquat H 100” by National Starch.

(4) the cationic polysaccharides disclosed more particularly in U.S.Pat. Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationictrialkylammonium groups. Use is made, for example, of guar gums modifiedby a 2,3-epoxypropyltrimethylammonium salt (for example, chloride).

Such products are sold in particular under the trade names of Jaguar C13S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by Meyhall.

(5) polymers composed of piperazinyl units and of divalent, straight- orbranched-chain alkylene or hydroxyalkylene radicals, optionallyinterrupted by oxygen, sulfur or nitrogen atoms or by aromatic orheterocyclic rings, as well as the oxidation and/or quaternizationproducts of these polymers. Such polymers are disclosed in particular inFrench Patents 2,162,025 and 2,280,361.

(6) water-soluble polyaminoamides prepared in particular bypolycondensation of an acidic compound with a polyamine; thesepolyaminoamides can be crosslinked by an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bisunsaturated derivative, abishalohydrin, a bisazetidinium, a bishaloacyldiamine or an alkylbishalide or alternatively by an oligomer resulting from the reaction ofa bifunctional compound reactive with respect to a bishalohydrin, abisazetidinium, a bishaloacyldiamine, an alkyl bishalide, anepilhalohydrin, a diepoxide or a bisunsaturated derivative; crosslinkingagent being used in proportions ranging from 0.025 to 0.35 mol per aminegroup of the polyaminoamide; these polyaminoamides can be alkylated or,if they comprise one or more tertiary amine functional groups,quaternized. Such polymers are disclosed in particular in French Patents2,252,840 and 2,368,508.

7) polyaminoamide derivatives resulting from the condensation ofpolyalkylenepolyamines with polycarboxylic acids, followed by analkylation by bifunctional agents. Mention may be made, for example, ofadipic acid/diakylaminohydroxyalkyldialylenetriamine polymers in whichthe alkyl radical comprises from 1 to 4 carbon atoms and preferablydenotes methyl, ethyl or propyl. Such polymers are disclosed inparticular in French Patent 1,583,363.

Mention may more particularly be made, among these derivatives, of theadipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers soldunder the name “Cartaretine F, F4 or F8” by Sandoz.

(8) polymers obtained by reaction of a polyalkylenepolyamine comprisingtwo primary amine groups and at least one secondary amine group with adicarboxylic acid chosen from diglycolic acid and saturated aliphaticdicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio ofpolyalkylenepolylamine to dicarboxylic acid being between 0.8:1 and1.4:1; the polyaminoamide resulting therefrom being brought to reactwith epichlorohydrin in a molar ratio of epichlorohydrin in relation tothe secondary amine group of the polyaminoamide of between 0.5:1 and1.8:1. Such polymers are disclosed in particular in U.S. Pat. Nos.3,227,615 and 2,961,347.

Polymers of this type are in particular sold under the name “Hercosett57” by Hercules Inc. or else under the name of “PD 170” or “Delsette101” by Hercules in the case of the adipicacid/epoxypropyl/diethylenetriamine [sic] copolymer.

(9) cyclohomopolymers of methyldiallylamine or ofdimethyldiallylammonium, such as the homopolymers comprising, as mainconstituent of the chain, units corresponding to the formulae (VI) or(VI′):

in which formulae k and t are equal to 0 or 1, the sum k+t being equalto 1; R₁₂ denotes a hydrogen atom or a methyl radical; R₁₀ and R₁₁,independently of one another, denote an alkyl group having from 1 to 22carbon atoms, a hydroxyalkyl group in which the alkyl group preferablyhas 1 to 5 carbon atoms or a lower amidoalkyl group or R₁₀ and R₁₁ candenote, jointly with the nitrogen atom to which they are attached,heterocyclic group, such as piperidinyl or morpholinyl; Y⁻ is an anion,such as bromide, chloride, acetate, borate, citrate, tartrate,bisulfate, bisulfite, sulfate or phosphate. These polymers are disclosedin particular in French Patent 2,080,759 and in its Certificate ofAddition 2,190,405.

Mention may more particularly be made, among the polymers defined above,of the dimethyldiallylammonium chloride homopolymer sold under the name“Merquat 100” by Merck.

(10) the quaternary diammonium polymer comprising repeat unitscorresponding to the formula:

in which formula (VII):

R₁₃, R₁₄, R₁₅ and R₁₆, which are identical or different, representaliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20carbon atoms or lower hydroxyalkyl aliphatic radicals or else R₁₃, R₁₄,R₁₅ and R₁₆, together or separately, form, with the nitrogen atoms towhich they are attached, heterocycles optionally comprising a secondheteroatom other than nitrogen or else R₁₃, R₁₄, R₁₅ and R₁₆ represent alinear or branched C₁-C₆ alkyl radical substituted by a nitrile, ester,acyl, amide or —CO—O—R₁₇-D or —CO—NH—R₁₇-D group, where R₁₇ is analkylene and D a quaternary ammonium group; A₁ and B₁ representpolymethylene groups comprising from 2 to 20 carbon atoms which can belinear or branched and saturated or unsaturated, and which can comprise,bonded to or inserted into the main chain, one or more aromatic rings orone or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide,amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or estergroups, and X⁻ denotes an anion derived from an inorganic or organicacid; A₁, R₁₃ and R₁₅ can form, with the two nitrogen atoms to whichthey are attached, a piperazine ring, in addition, if A₁ denotes alinear or branched, saturated or unsaturated alkylene or hydroxyalkyleneradical, B₁ can also denote a (CH₂)_(n)—CO-D-OC—(CH₂)_(n) group in whichD denotes:

a) a glycol residue of formula: —O—Z—O—, where Z denotes a linear orbranched hydrocarbon-comprising radical or a group corresponding to oneof the following formulae:—(CH₂—CH₂—O)_(x)—CH₂—CH₂——[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—where x and y denote an integer from 1 to 4, representing a defined andunique degree of polymerization, or any number from 1 to 4 representinga mean degree of polymerization;

b) a bis-secondary diamine residue, such as a piperazine derivative;

c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y denotesa linear or branched hydrocarbon-comprising radical or else the divalentradical —CH₂—CH₂—S—S—CH₂—CH₂—;

d) a ureylene group of formula: —NH—CO—NH—; preferably, X⁻ is an anion,such as chloride or bromide.

These polymers have a number [lacuna] molecular mass generally ofbetween 1000 and 100,000.

Polymers of this type are disclosed in particular in French Patents2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and U.S. Pat.Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002,2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193,4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

(11) polymers of poly(quaternary ammonium) composed of units of formula(VIII):

in which formula:

R₁₈, R₁₉, R₂₀ and R₂₁, which are identical or different, represent ahydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl,β-hydroxypropyl or —CH₂CH₂ (OCH₂CH₂)_(p)OH radical,

where p is equal to 0 or to an integer of between 1 and 6, with theproviso that R₁₈, R₁₉, R₂₀ and R₂₁ do not simultaneously represent ahydrogen atom,

r and s, which are identical or different, are integers of between 1 and6,

q is equal to 0 or to an integer of between 1 and 34,

X denotes a halogen atom,

A denotes a radical from a dihalide or preferably represents—CH₂CH₂—O—CH₂—CH₂—.

Such compounds are disclosed in particular In Patent ApplicationEP-A-122,324.

Mention may be made among these, for example, of the products “Mirapol A15”, “Mirapol AD1”, “Mirapol AZ1” and “Mirapol 175”, sold by Miranol.

(12) homopolymers or copolymers derived from acrylic or methacrylicacids and comprising units:

in which the R₂₂ groups independently denote H or CH₃, the A₁ groupsindependently denote a linear or branched alkyl group of 1 to 6 carbonatoms or a hydroxyalkyl group of 1 to 4 carbon atoms,the R₂₃, R₂₄ and R₂₅ groups, which are identical or different,independently denote an alkyl group of 1 to 18 carbon atoms or a benzylradical,

the R₂₆ and R₂₇ groups represent a hydrogen atom or an alkyl group of 1to 6 carbon atoms,

X₂ ⁻ denotes an anion, for example methyl sulfate or halide, such aschloride or bromide.

The comonomer or comonomers which can be used in the preparation of thecorresponding copolymers belong to the family of acrylamides,methacrylamides, diacetone acrylamides, acrylamides and methacrylamidessubstituted at the nitrogen by lower alkyls, alkyl esters, of acrylic ormethacrylic acids, vinylpyrrolidone or vinyl esters.

(13) quaternary polymers of vinylpyrrolidone and of vinylimidazole, suchas, for example, the products sold under the names Luviquat FC 905, FC550 and FC 370 by B.A.S.F.

(14) polyamines, such as Polyquart H sold by Henkel, referenced underthe name “Polyethylene Glycol (15) Tallow Polyamine” in the CTFAdictionary.

(15) crosslinked polymers of methacryloyloxyethyltrimethylammoniumchloride, such as the polymers obtained by homopolymerization ofdimethylaminoethyl methacrylate quaternized by methyl chloride or bycopolymerization of acrylamide with dimethylaminoethyl methacrylatequaternized by methyl chloride, the homo- or copolymerization beingfollowed by a crosslinking by a compound possessing olefinicunsaturation, in particular methylenebisacrylamide. Use may moreparticularly be made of a crosslinkedacrylamide/methacryloyloxyethyltrimethylammonium chloride (20/80 byweight) copolymer in the form of a dispersion comprising 50% by weightof the said copolymer in mineral oil. This dispersion is sold under thename of “Salcare SC 92” by Allied Colloids. Use may also be made of acrosslinked homopolymer of methacryloyloxyethyltrimethylammoniumchloride comprising approximately 50% by weight of the homopolymer inmineral oil. This dispersion is sold under the name of “Salcare SC 95”by Allied Colloids.

Other cationic polymers which can be used in the context of theinvention are polyalkyleneimines, in particular polyethyleneimines,polymers comprising vinylpyridine or vinylpyridinium units, condensatesof polyamines and of epichlorohydrin, quaternary polyureylenes andchitin derivatives.

According to the invention, use may more particularly be made ofpolymers chosen from Mirapol, the compound of formula (VII) in whichR₁₃, R₁₄, R₁₅ and R₁₆ represent the methyl radical, A₁ represents theradical of formula —(CH₂)₃— and B₁ represents the radical of formula—(CH₂)₆— and X⁻ represents the chloride anion (subsequently referred toas Mexomere PO) and the compound of formula (VII) in which R₁₃ and R₁₄represent the ethyl radical, R₁₅ and R₁₆ represent the methyl radical,A₁ and B₁ represent the radical of formula —(CH₂)₃— and X⁻ representsthe bromide anion (subsequently referred to as Mexomere PAK).

Preference is given, among all the cationic polymers which can be used,to the use of the compounds described above in points (3) and (4).

According to the invention, the cationic polymer or polymers canrepresent from 0.001% to 10% by weight, preferably from 0.005% to 5% byweight and more preferably still from 0.01% to 3% by weight of the totalweight of the final composition.

The aqueous medium can comprise, in addition to water, cosmeticallyacceptable solvents other than the propenetrating agent, such asmonoalcohols, polyalcohols or glycol ethers, used alone or as a mixture.

Mention may more particularly be made, among these solvents, ofpolyethylene glycol, glycerol and sorbitol. The solvents are preferablyused in proportions of 0.5 to 10% by weight with respect to the totalweight of the composition.

The pH of the compositions is preferably between 2 and 9 and inparticular between 3 and B. For clobetasol propionate, the pH isadvantageously between 5.5 and 6.5. It is adjusted with cosmeticallyacceptable basifying or acidifying agents.

The compositions according to the invention can additionally compriseother adjuvants used in foaming compositions, such as shampoos, and inparticular ceramides, such as those disclosed in French Patent FR 2 673179, glycoceramides, or well-known nonionic surfactants which can bechosen from polyethoxylated, polypropoxylated or polyglycerolatedalcohols, α-diols, alkylphenols or fatty acids with a fatty chaincomprising, for example, 8 to 18 carbon atoms, it being possible for thenumber of ethylene oxide and propylene oxide groups to range inparticular from 2 to 50 and it being possible for the number of glycerolgroups to range in particular from 2 to 30. Mention may also be made ofcopolymers of ethylene oxide and of propylene oxide or condensates ofethylene oxide and of propylene oxide with fatty alcohols;polyethoxylated fatty amides preferably having 2 to 30 mol of ethyleneoxide or polyglycerolated fatty amides comprising on average 1 to 5glycerol groups and in particular 1.5 to 4 glycerol groups;polyethoxylated fatty amines preferably having 2 to 3 mol of ethyleneoxide; oxyethylenated fatty acid esters of sorbitan having from 2 to 30mol of ethylene oxide; fatty acid esters of sucrose, fatty acid estersof polyethylene glycol, alkylpolyglycosides, N-alkylglycaminederivatives, or amine oxides, such as (C₁₀-C₁₄)alkylamine oxides orN-acylaminopropylmorpholine oxides. Alkylpolyglycosides andpolyglycerolated alcohols, α-diols, alkylphenols or of [sic] fatty acidsare more particularly preferred.

The compositions can also comprise thickening agents chosen inparticular from sodium alginate, gum arabic, cellulose derivatives, suchas methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose,hydroxylpropylcellulose or hydroxypropylmethylcellulose, guar gum or itsderivatives, xanthan gums, scleroglucans, crosslinked polyacrylic acids,polyurethanes, copolymers based on maleic acid or anhydride, orassociative thickeners carrying fatty chains of natural type, such asthe product sold under the name Natrasol Plus, or synthetic type, suchas the products sold under the name Pemulen.

The thickener can also be obtained by mixing polyethylene glycol andpolyethylene glycol stearates or distearates or mixing amides andphosphoric esters.

The compositions in accordance with the invention can also comprisecolorants, viscosity-modifying agents, pearlescent agents, moisturizingagents, antidandruff agents, antiseborrheic agents, sunscreens,proteins, vitamins, α-hydroxy acids, salts, fragrances, preservatives,sequestering agents, softeners, foam modifiers, detoxifying agents ortheir mixtures.

Conditioning agents can also be used, such as hydrogenated ornonhydrogenated and synthetic or nonsynthetic natural hydrocarbonaceousoils which are cyclic or aliphatic and linear or branched (saturated orunsaturated), volatile or nonvolatile, organomodified ornonorganomodified and soluble or insoluble silicones, perfluorinated orfluorinated oils, polybutenes and polyisobutenes, fatty esters which areprovided in a liquid, pasty or solid form, esters of polyhydricalcohols, glycerides, natural or synthetic waxes, silicone gums andresins, quaternary ammonium salts, such as, for example, the compoundclassified in the CTFA dictionary, 7th edition, 1998, under the nameQuaternium-22 and sold under the name “Ceraphyl 60”, or the mixture ofthese various agents.

In the context of the present invention, the compositions are moreparticularly in the form of liquids, optionally thickened liquids.

They can be used as they are or can be diluted before use.

The compositions in accordance with the invention are more particularlyused as shampoos for treating the hair or the scalp.

In this case, the composition is preferably applied to wet or dry hair,gentle massaging is then carried out, during which a foam is formed,rinsing is then carried out and, optionally, the shampoo is applied afurther time, followed by a further rinsing with water.

A subject matter of the invention is consequently a foaming compositionas defined above for its application as medicament.

Another subject matter of the present invention is the use of acomposition as defined above in the manufacture of a medicament intendedfor the treatment of ailments of the scalp.

The compositions according to the invention are very particularlyindicated in the treatment of eczemas, eczematous or psoriaticerythrodermas, pruriginous lesions, chronic lupus erythematosus,psoriasis and parapsoriasis en plaque.

These treatments generally require an application as described above 2to 3 times per week.

Several examples of compositions according to the invention will now begiven by way of illustration and without any limiting nature.

EXAMPLE I

The following shampoo is prepared:

Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Transcutol ® (ethoxydiglycol) 10 g Clobetasol propionate 0.05 g JaguarC162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride) Lacticacid q.s. pH 6 Demineralized water q.s. 100 g

EXAMPLE II

The following shampoo is prepared:

Dehyton AB 30 (cocoyl betaine 6 g comprising 32% A.M.) Jaguar C162 ®(hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride) Sipon AOS 225UP ® (sodium lauryl 43 g ether sulfate comprising 28% A.M.) Ethanol(95/96%) 10 g Clobetasol propionate 0.05 g Benzalkonium chloride 0.005 gLactic acid q.s. pH 6 Demineralized water q.s. 100 g

EXAMPLE III

The following shampoo is prepared:

Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Transcutol ® (ethoxydiglycol) 10 g Adapalene 0.05 g Jaguar C162 ®(hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride) Lactic acidq.s. pH 6 Demineralized water q.s. 100 g

EXAMPLE IV

The following shampoo is prepared:

Sipon AOS 225 UP ® (sodium lauryl 43 g ether sulfate comprising 28%A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 31% A.M.) Ethanol(95/96%) 10 g Benzalkonium chloride 0.01 g Jaguar C162 ®(hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride) Clobetasolpropionate 0.05 g Lactic acid q.s. pH 6 Demineralized water q.s. 100 g

EXAMPLE V

The following shampoo is prepared:

Celquat SC 240 ® (polyquaternium 10) 2 g Texapon N70 ® (sodium laurylether 17 g sulfate (2 mol EO) comprising 70% A.M.) Dehyton AB 30 ®(cocoyl betaine 6 g comprising 32% A.M.) Rewoquat B50 ® (50%benzalkonium 0.01 g chloride) Citric acid•1H₂O 0.24 g Sodiumcitrate•2H₂O 2.6 g Ethanol (95/96%) 10 g Clobetasol propionate 0.05 gDemineralized water q.s. 100 g

EXAMPLE VI

The following shampoo is prepared:

Celquat SC 240 ® (polyquaternium 10) 2 g Texapon N70 ® (sodium laurylether 17 g sulfate (2 mol EO) comprising 70% A.M.) Dehyton AB 30 ®(cocoyl betaine 6 g comprising 32% A.M.) Rewoquat B50 ® (50%benzalkonium 0.01 g chloride) Ethanol (95/96%) 10 g Clobetasolpropionate 0.05 g Demineralized water q.s. for 100 g

EXAMPLE VII

The following shampoo is prepared:

Citric acid•1H₂O 0.24 g Sodium citrate•2H₂O 2.6 g Methylpara-hydroxybenzoate 0.1 g Celquat SC 240 ® (polyquaternium 10) 2 gTexapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Clobetasol propionate 0.05 g Ethanol (95/96%) 10 g Purified water q.s.for 100 g

EXAMPLE VIII

The following shampoo is prepared:

Citric acid 0.24 g Sodium citrate 2.6 g Celquat SC 240 ® (polyquaternium10) 2 g Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO)comprising 70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32%A.M.) Clobetasol propionate 0.05 g Ethanol (95/96%) 10 g Purified waterq.s. for 100 g

EXAMPLE IX

The following shampoo is prepared:

Jaguar C162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride)Chimexane HC (cocoyl betaine 6.0 g comprising 32% A.M.) Sipon AOS 225UP ® (sodium lauryl 43.0 g ether sulfate comprising 28% A.M.) Ethanol(95/96%) 10.0 g Clobetasol propionate 0.05 g Rewoquat B50 (50%benzalkonium 0.01 g chloride) Purified water q.s. for 100 g

EXAMPLE X

The following shampoo is prepared:

Jaguar C162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride)Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Rewoquat B50 ® (50% benzalkonium 0.01 g chloride) Ethanol (95/96%) 10 gAdapalene 0.05 g Demineralized water q.s. for 100 g

EXAMPLE XI

The following shampoo is prepared:

Jaguar C162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride)Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Rewoquat B50 ® (50% benzalkonium 0.01 g chloride) Ethanol (95/96%) 10 g4-[7-(1-Adamantyl)-6- 0.05 g methoxyethoxymethoxy-2- naphthyl]benzoicacid Demineralized water q.s.for 100 g

EXAMPLE XII

The following shampoo is prepared:

Jaguar C162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride)Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Rewoquat B50 ® (50% benzalkonium 0.01 g chloride) Ethanol (95/96%) 10 g2-Hydroxy-4-[3-oxo-3-(3-tert-butyl- 0.05 g4-methoxyphenyl)-1-propynyl]benzoic acid Demineralized water q.s.for 100g

EXAMPLE XIII

The following shampoo is prepared:

Jaguar C162 ® (hydroxypropylguar 0.5 g hydroxypropyltrimonium chloride)Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Rewoquat B50 ® (50% benzalkonium 0.01 g chloride) Ethanol (95/96%) 10 g4-(3,5,5,8,8-Pentamethyl-5,6,7,8- 0.05 gtetrahydro-2-naphthylthio)benzoic acid Demineralized water q.s.for 100 g

EXAMPLE XIV

The following shampoo is prepared:

Texapon N70 ® (sodium lauryl ether 17 g sulfate (2 mol EO) comprising70% A.M.) Dehyton AB 30 ® (cocoyl betaine 6 g comprising 32% A.M.)Methocel E4M 1 g (hydroxypropylmethylcellulose) Citric acid•1H₂O 0.24 gSodium citrate•2H₂O 2.6 g Ceraphyl 60 (quaternium 22) 0.5 g Clobetasolpropionate 0.05 g Ethanol (95/96%) 10 g Demineralized water q.s. 100 g

The compositions of Examples I to XIV above are stable on storage andexhibit a satisfactory foaming effect.

A clinical study, in which a composition according to Example IX wasused as shampoo once daily for two weeks, the shampoo being applied towet hair and left in contact for 10 minutes in order to be subsequentlyrinsed out, made it possible to observe in patients suffering frompsoriasis a reduction on the scalp of erythemas of 37%, of desquamationof 47%, of hyperkeratoses of 50% and of pruritides of 57%.

1. A stable shampoo for washing and treating hair and/or scalpconsisting of: 0.05 wt % of clobetasol propionate, 2 to 25 wt % ofsodium lauryl ether sulphate, 1 to 15 wt % of cocoyl betaine; 2 wt % ofpolyquaternium 10, 10 wt % of ethanol (95%-96%), citric acid and sodiumcitrate in an amount required to adjust the pH of said composition tobetween 5.5 and 6.5, and q.s. for 100% water.
 2. A stable shampoo forwashing and treating hair and/or scalp consisting of: 0.05 wt % ofclobetasol propionate, 2 to 25 wt % of sodium lauryl ether sulphate, 1to 15 wt % of cocoyl betaine; 2 wt % of polyquaternium 10 or 0.5 wt %cationic guar gum, 10 wt % of ethanol (95%-96%), citric acid and sodiumcitrate in an amount required to adjust the pH of said composition tobetween 5.5 and 6.5, and q.s. for 100% water.
 3. A stable shampoo forwashing and treating hair and/or scalp consisting of: 0.05% ofclobetasol propionate, 2 to 25 wt % of sodium lauryl ether sulphate, 1to 15 wt % of cocoyl betaine; 0.01 to 3 wt % of cationic guar gum orpolyquaternium 10, 10 wt % of ethanol (95%-96%), cosmetically acceptablebasifying or acidifying agents in an amount to adjust the pH of saidcomposition to between 5.5 and 6.5, and q.s. for 100% water.
 4. Thestable shampoo of any one of claims 1-3 wherein the ratio of the amountof sodium lauryl ether sulphate in said composition to the amount ofcocoyl betaine in said composition is in the range of 1-20.
 5. Thestable shampoo of any one of claims 1-3 wherein the ratio of the amountof sodium lauryl ether sulphate in said composition to the amount ofcocoyl betaine in said composition is 2 to
 10. 6. The stable shampoo ofany one of claims 1-3 wherein the ratio of the amount of sodium laurylether sulphate in said composition to the amount of ethanol in saidcomposition is 1 to 2.